Monoazo dyestuffs



United States Patent 3,122,532 MGNGAZG DYESTUFFS Meinrad Hiirbin andGuido Schetty, both of Basel, Switzerland, assignors to .l. R. GeigyA.-G., Basel, Switzerland No Drawing. Filed Oct. 1%, 1961, Ser. No.144,023 Claims priority, application Switzerland Oct. 11, 1960 5 Claims.(61. 259-199) The present invention concerns new monoazo dye- I stuffs,processes for the production thereof as well as their use for the dyeingof keratin material, in particular, of wool. The invention alsoconcerns, as industrial product, the materials dyed with the aid ofthese dyestuffs.

Monoazo dyestuffs obtained from diazotised aminophenoxybenzene compoundsthe phenoxy radical of which contains an aliphatic, cycloaliphatic,araliphatic or aromatic radical having at least 4 carbon atoms, andl-acylamino-8-hydroxynaphthylene sulphonic acids as coupling componentshave already been described. These dyestufifs dye wool in fast redshades.

It has now been found that monoazo dyestufis having greatly increasedwet fastness properties and also improved fastness to light are obtainedif a diazotised aminophenoxyhenzene compound, the phenoxy radical ofwhich is substituted by an aliphatic, cycloaliphatic, araliphatic oraromatic radical having at least 4 carbon atoms and the benzene nucleiof which can contain further nonionogenic substituents, is coupled in aweakly acid, neutral or weakly alkaline medium with a coupling componentof the general Formula I 5 4 S 03H (I) wherein R represents hydrogen orthe methyl group, Hal represents halogen, particularly chlorine, and nis l or 2.

NH-CO- (CH2) nHal SOsH (II) in which the benzene nucleus A issubstituted by at least one aliphatic, cycloaliphatic, araliphatic oraromatic radical containing at least 4 carbon atoms and in which thebenzene nuclei A and B can contain further non-ionogenic substituents, Ris hydrogen or the methyl group, Hal is halogen and n is l or 2.

Examples of the radical containing at least 4 carbon atoms in theaminophenoxybenzene compounds used according to the invention are butyl,amyl, hexyl or octyl groups, the cycloaliphatic radical is principallythe cyclohexyl group and mainly the benzyl group is used as araliphaticradical and the phenyl group is aromatic radical. This radicalcontaining at least 4 carbon atoms is advantageously in the p-positionto the phenoxy group.

"ice

The aminophenoxy benzene compounds used as diazo components according tothe invention can contain, as further nonionogenic substituents, forexample low alkyl groups such as methyl, ethyl or propyl groups, lowalkoxy groups such as methoxy or ethoxy groups, halogens such asfluorine, chlorine or bromine, nitro groups, sulphonyl groups such asmethylsulphonyl, ethylsulphonyl, propylsulphonyl or phenylsulp'nonylgroups, sulphonic acid amide or sulphonic acid ester groups orcarboxylic acid amide groups or nitrile groups.

The diazotised aminophenoxybenzene compounds are coupled with thecoupling components of general Formula I by the usual methods,preferably in an acetic acid medium and the monoazo dyestuflis so formedaccording to the invention are isolated in the form of their alkalimetal salts, in particular in the form of the sodium salts.Aminophenoxybenzene compounds having the phenoxy radical in 0- orp-position to the amino group, are preferred.

Examples of amincphenoxybenzene compounds which can be used according tothe invention are:

2-, 3- or 4-amino-l-(2'-, 3 or 4-n-butyl-phenoXy)-benzene,

2-, 3- or 4-amino-l-(2-, 4'-di-n-butyl-phenoxy)-benzene,

2-, 3- or 4-amino-1-(2-methyl-4'-n-butyl-phenoxy)-benzene,

2-, 3- or 4-amino-l-(2- or 4'-isobutyl-phenoxy)-benzene,

2-, 3- or 4-amino-1-(4'-tert. butyl-phenoxy)-benzene,

2-, 3- or 4-amino-l-(2'-methy1-4-tert. butyl-phenoxy)- benzene,

2-, 3- or 4-amino-l-(4'-amyl-phenoxy)-benzene,

2-, 3- or 4-amino-1-(2-methyl-4'-amyl-phenoxy)benzene,

2-, 3- or 4-amino-1-(4-n-hexyl-phenoxy)-benzene,

2-, 3- or 4-amino-l-(4'-octyl-phenoxy)-benzene,

2-, 3- or 4-amino-l-(4'-cyclohexyl-phenoxy)-benzene,

2-, 3- or 4-amino-l-(4'-benzyl-phenoxy)-benzene,

2-, 3- or 4-amino-1-(4-o-chlorobenzyl-phenoxy)-benzene,

2-, 3- or 4-amino-l-(4'--m-chlorobenzyl-phenoxy) Phenzene,

2-, 3- or 4-amino-1-(4'-p-chlorobenzyl-phenoxy) -benzene,

2-, 3- or 4-amino-l-(2'- or 4-phenyl-phenoxy)-benzene,

2-, 3- or 4-amino-1-(4-isoamyl-phenoxy)benzene,

2-amino-4- or -5-methyl-1-(2'- or 4'-arnyl-phenoxy)-ben zene,

2-amino-4,5-dimethyl-l-(2'- or 4-amyl phenoxy) benzene,

2-amino-4- or -5-chloro-1-(2'- or 4-amyl-phenoxy)-ben zene, or

2-amino-4,5-dichloro-1-(2'- or 4-amy1 phenoxy) benzene.

Those aminophenoxybenzene compounds are preferred which have the phenoxyradical in 0- or p-position to the amino group.

The coupling components of Formula I are obtained, for example, byreacting 1-amin0-8-hydroxy-3,6- or -4,6- disulphonic acid with acompound of the general Formula III N02 (III) wherein R and Hal have themeanings given above, the reaction being performed advantageously inaqueous-organic solution at a pH of about 4.5, possibly in the presenceof a buffer salt, advantageously an alkali metal salt of a low fattyacid, in particular sodium acetate, then reducing the nitro group to theamino group and reacting, advantageously under the conditions mentionedfor the a first step, witha halogen fatty acid halide of the generalFormula 1V Hal-CO(CH Hal HOzS- 7 in which:

R rep-resents an alkyl group having 4 to 8 carbon atoms,

phenyl, benzyl or a cyclohexyl group,

R represents hydrogen or the methyl group,

R represents hydrogen or the methyl group which is bound in a positionmeta, para or ortho to the O-linkage,

X represents chlorine or the methyl radical,

n represents an integer from to 2 inclusive,

Z represents a chloroacetylamino or a brornoacetylamino group which isbound in metaor para-position to the O linkage and the second sulphonicacid group of the naphthalene nucleus is in 3- or 4-position.

Of the foregoing particularly good dyestuffs, the monoazo dyestuffshaving the general formula no un-oo-orn-o-O SOaH are especiallyvaluable.

The new monoazo dyestufis dye fibres containing nitrogen principallykeratin fibres, particularly wool, but also silk, or leather, from aneutral, but mainly from a weakly aoid bath in level red shades. Thesedyestuffs may possibly be mixed with slight amounts of basic salts, inparticular with alkali phosphates such as, e.g. trisodium phosphate ortetrasodium pyrophosphate or with wetting agents having a dispersingaction such as, e.g. higher alkyl-aryl sulphonates orpolyalkyleneoxy-fatty acid condensation products to improve the Watersolubility.

The W001 dyeings attained with the new monoazo dyestuffs differ fromthose of similar known monoazo dyel studs in their better wet fastnessproperties, in particular their fastness to Washing, milling and seawater. They also have increased fastness to light and some of them havea more pure shade.

The following examples illustrate the invention. Where 7 not otherwisestated, parts are given as parts by Weight. The temperatures are indegrees centigrade. The relationship of parts by weight to parts byvolume is as that of kilogrammes to litres.

EXAMPLE 1 no rrrr-oowm-o-O l (1) H0 8 SO3H 25.5 parts of 4'-tert.amyl-Z-aminodiphenyl ether are dissolved in pants of ethyl alcohol and30 parts of concentrated hydrochloric acid and diazotized by thedropwise addition of a solution of 6.9 parts of sodium nitrite in 15parts of water at 07. The diazo solution so obtained is poured at 05into a solution of the disodium salt of 54.45 parts ofl-[(3'-chloroacetylamino)- p henoxyacetylamino] 8hydroxynaphthalene-ll,6-disulphonic acid and 24 parts of sodiumbicarbonate in 1800 parts of water. The Whole is stirred for severalhours, 12 parts of concentrated hydrochloric acid are added dropwise andthe precipitated dyestuff is filtered off and dried. It is a red powderwhich dyes wool from a neutral to weakly acid bath in pure red shadeswhich are fast to light, rubbing, and wet.

EXAMPLE 2 HCI) ITIH-CO-CHz-O- N=N- NH-C O-O Ha-Cl S O all 25.5 parts of4'-tent. amyl-Z-amino-diphenyl other are dissolved in 120 parts of ethylalcohol and 30 parts of concentrated hydrochloric acid, and diazotizedby the dropwise addition, at 0-7, of a solution out 6.9 parts of sodiumnitrite in parts of water. The diazo solution is poured at 05 into asolution of the disodi-um salt of 54.45 parts ofl-[(3-chloroacetylamino)-phenoxyacetylamino]-8-hydroxynaphthalene-4,6-disulphonicacid and 22 parts of sodium carbonate in 1600 parts of water. The wholeis stirred for several hours, parts of concentrated hydrochloric acidare added, the precipitated dyestuif -is filtered oil and dried. It is ared powder which dissolves in hot water with a vivid red colour. It dyeswool from a neutral to weakly acid bath in pure red shades which arefast to light and rubbing and have excellent fastness to washing,milling and sea water.

Similar dyestuffs are obtained if, in the above example, 63.3 parts ofthe disodiurn salt of 1-[(3-bromoacetylamino) -phenoxyacetylamino] 8hydroxynaphthalene- 4,6-disulphonic acid or 60.25 parts of the disodiumsalt of l-[ (3' chloropropiony-lamino)-phenoxyacetylarnino]-8-hydroxynaphthalene-4,6-disulphonic acid are used as couplingcomponent.

EXAMPLE 3 A solution of 6.9 parts of sodium nitrite in 16 parts of wateris added dropwise at 3-7 to a solution of 25.5 parts of 4-tert.amyl-4-aminodiphenyl ether in 100 parts of ethyl alcohol and parts ofconcentrated hydrochloric acid. The diazo solution so obtained is pouredat 05 into a solution of the disodium salt of 54.45 parts of 1- [(3-chloroacetylamino)-phenoxyacetylamino]-8-hydroxynaphthalene-3,6-disulphonic acid and 28 parts of crystallisedsodium acetate in 2000 parts of Water. The whole is stirred for severalhours, the precipitated dyestuff is filtered off and dried. It is a darkred powder which dyes wool from a neutral to weakly acid bath in pureblueish red shades which are fast to wet and light.

EXAMPLE 4 25.5 parts of 4-tert. amyI-Z-aminodiphenyl ether are dissolvedin 120 parts of ethyl alcohol and '30 parts of concentrated hydrochloricacid and diazotised by the dropwise addition of a solution of 6.9 partsof sodium nitrite in 16 parts of water at 07. The diazo solution I NH-CO-CHz-Cl H O as l SOgH A solution of 6.9 parts of sodium nitrite in 16parts of water is added dropwise at 37 to a solution of 25.5 parts of4-tert. arnyl-4-aminodiphenyl ether in 120 parts of ethyl alcohol and 30parts of concentrated hydrochloric acid. The diazo solution so obtainedis poured at 05 into a solution of the disoclium salt of 54.45 parts of1 (3-chloroacetylamino) -phenoxyacetylamino]-8-hydroxynaphthalene-4,6-disulphonic acid and 28 parts of crystallisedsodium acetate in 2000 parts of Water. The Whole is stirred for severalhours, 40 parts of sodium chloride are sprinkled in and the precipitateddyestuff is filtered oil and dried. It is a dark red powder which dyeswool from a neutral to weakly acid bath in pure red shades which arefast to wet and light.

EXAMPLE 6 26.9 parts of 4'-tert. amyl-4-rnethyl-2-aminodiphenyl etherare dissolved in 150 parts of ethyl alcohol and 30 parts of concentratedhydrochloric acid and a solution of 6.9 parts of sodium nitrite in 16parts of water is slowly added dropwise at -7 while stirring. The diazosolution so obtained is poured at 05 into a solution of the disodiumsalt of 54.45 parts of 1-[(3-chloroacetylamino)- phenoxyacetylamino] 8hydroXynaphthalene-4,6-disulphonic acid and 28 parts of crystallisedsodium acetate in 2000 parts of water. The whole is stirred for severalhours, then 60 parts of sodium chloride are sprinkled in, theprecipitated dyestutf is filtered oil and then dried. It is a red powderwhich dyes Wool from a neutral to weakly acid bath in pure red shadeswhich are fast to wet and light.

EXAMPLE 7 25.5 parts of 4-tert. amyl-3-aminodiphenylether are dissolvedin 120 parts of ethyl alcohol and 30 parts of concentrated hydrochloricacid and diazotised by the dropwise addition of a solution of 6.9 partsof sodium nitrite in 16 parts of water at 0-7 The diazo solution soobtained is poured at O5 into a solution of the disodium salt of 54.45parts of l-[(3'-chloroacetyla1m'no)-phenoxyacetylarnino]-8-hydroxynaphthalene-4,6-disulphonicacid amino]-8-hydroxynaphthalene-3,6-disulphonic acid and 30 parts ofcrystallised sodium acetate in 2000 parts of,

water. The whole is stirred for several hours, heated to and parts ofsodium chloride are sprinkled in. The precipitated dyestuff is filteredoil and dried. It is a red powder which dyes wool from a neutral toweakly acid bath in pure bluish red shades which are fast to wet andlight.

EXAMPLE 9 I SOJH ls n 25.5 parts of 4-tert. amyl-2-aminodiphenyl etherare dissolved in parts of ethyl alcohol and 30 parts of concentratedhydrochloric acid and diazotised by the dropwise addition of a solutionof 6.9 parts of sodium nitrite in 15 parts of water at 07. The diazosolution so obtained is poured at 05 into a solution of the disodiumsalt of 55.85 parts of l-[ (3'-chloroacetylannno-4'-methyl)-phenoxyacetylamino] 8 hydroxynaphthalene 4,6 disulphonic acid and 22parts of sodium carbonate in 1600 parts of water. The whole is stirredfor several hours, 25 parts of concentrated hydrochloric acid are pouredin, the precipitated dyestufi is filtered 0E and dried. It is a redpowder which dissolves in hot water with a vivid red colour and dyeswool from a neutral to weakly acid bath in pure red shades which arefast to light and rubhing and have excellent fastness to washing,milling and sea water.

EXAMPLE 10 and 30 parts of crystallised sodium acetate in 1800 parts ofwater. The whole is stirred for several hours, 60 parts of sodiumchloride are sprinkled in and the precipitated dyestuff is filtered offand dried. It dyes wool from a neutral to weakly acid bath in pure redshades which are fast to wet and light.

EXAMPLE 8 31 parts of 4'-butyl-4,5-dichloro-Z-arninodiphenyl ether aredissolved in 200 parts of ethyl alcohol and 30 parts of concentratedhydrochloric acid and diazotised by the dropwise addition of a solutionof 6.9 parts of sodium nitrite in 16 parts of water at 0-7". The diazosolution is poured at 0-5 into a solution of the disodium salt of v54.45 parts of l-[(3-chloroacetylan1ino)-phenoxyacetyl- SOsH- SOaH Asolution of 6.9 parts of sodium nitrite in 16 parts of water is addeddropwise at 3-7 to a solution of 25.5 parts of 4'-tert.amyl-4-aminodiphenyl ether in 100 parts of ethyl alcohol and 30 parts ofconcentrated hydro chloric acid. The diazo solution so obtained ispoured at 0-5 into a solution of the disodium salt of 55.85 parts of1-[(3'-chloroacetylamino 4' methyl)-phenoX-yacetyleamino]-8-hydroxynaphthalene-3,6-disulphonic acid and 28 parts ofcrystallised sodium acetate in 2000 parts of water. The whole is stirredfor several hours and the precipitated dyestuff is filtered olf anddried. It is a dark red powder and dyes wool from a neutral to weaklyacid bath in pure blueish red shades which are fast to wet and light.

EXAMPLE 11 H? ITUE-CO-CHg-OGCHB 26.9 parts of 2'-methyl-4'-tert.amyl-Z-amino-diphenyl ether are dissolved in 120 parts of ethyl alcoholand 30 parts of concentrated hydrochloric acid and diazotised by thedropwise addition at O7 of 6.9 parts of sodium nitrite in 15 parts ofwater. The diazo solution so obtained is poured at 5 into a solution ofthe disodium salt of 55.85 parts of1-[(3-chloroacetylamino-4'-metl1yl)-phenoxyacetylamino] 8hydroxynaphthalene 4,6 disulphonic acid and 22 parts of sodium carbonatein 1600 parts of water. The whole is stirred for several hours, 25 partsof concentrated hydrochloric acid are added and the precipitateddyestuif is filtered off and dried. It is a red powder which dissolvesin hot water with a vivid red colour and dyes wool from a neutral toweakly acid acid bath in pure red shades which are fast to light andrubbing.

A similar dyestufi is obtained if, in the above example, 25.5 parts of2-methyl-4-tert. butyl-Z-amino-diphenylether are used as diazo componentinstead of 26.9 parts of 2'-methyl-4-tert. amyl-Z-arnino-diphenyl ether.

Further dyestufis are given in the following table which are obtained bythe methods described in Examples 1 to 11.

Table No. Diazo component Azo component shadelof woo dyeing 1 4-tert.amyl-2-aminol-[(4-bromoacetylamin0)- Red. diphenyl ether.phen0xyacetylarnino1-8- hydroxynaphthalene-4,6- disuiphonic acid.

2- 4-tert. amyH-amino- 1[(3-bromoacetylamino)- Blueish diphenylether.phenoxyacetylamino1-8- red.

hydroxynaphthalene4,d disulphonic acid.

3- e n-hexyl-lamino- 1-[ (3-ch loroacetylamino)- Red.

diphenyl ether. phenoxyacetylaminfld hydroxynaphthalcne-3,6- disulphonicacid.

4- do 1[(3bromoacetylamino)- Do.

phenoxyacetylamino1-8- hydroxynaphthalene-3,6- disulphonic acid.

5- 4 phenyl-2amino- 1-[(3-bron1oacetylarn.in0)- D0.

diphenyl ether. phenoxyacetylaminoI-fihydroxynaphthalene-4,6-disulphonic acid.

6 do 1-[(3-chl0roacetylamino)- Do.

phenoxyacetylamino1-8- hydroxynaphtha1ene-4,6- disulphonic acid.

7 4-octyl-2-arninodido Do.

phenyl ether.

8 do 1-[(3-bromoacetylamino)- Do.

phenoxyaeetylamino1-8- hydroxynaphthalene-4,6- disulphonic acid.

9 4-benzyl-2-a.minod0 Do.

diphenyl ether.

10--.- do 1-[(3-chloroacetylamino)- Do.

phenoxyacetylamino]-8- hydroxynaphthalene-4,6- disulphonic acid.

11 i 4-cyclohexyl-2-amino do Do.

diphenyl ether.

12 do 1-[(3'-bromoacetylamino)- Do.

phenoxyacetylaminolik hydroxynaphthalene-4,6- disulphonic acid.

18 4-buty1-2-amino- 1-[(3-chloroacety1amino)- Do.

diphenyl ether. phenoxyacctylamino]-8- hydrownaphthalenei, 6-disulphonicacid. 14 4-butyl-4,5-dichlorodo Do.

2-aminodiphenyl ether.

l5 4'-butyl4,5-dimethyldo Do.

Z-aminodiphenyl ether.

16 4-tert.amyl-4chlorodo Do.

2-aminodiphenyl ether.

17. 4-tert.amyl-4-methyl- 1-[(3-ch1oroacetylamino) Do.

Z-aminodiphenyl phenoxyacetylamino1-8- ether. hydroxynaphthalene-3,

G-disulphonic acid.

1s 4-tert.amylt,5-dido Do.

methyl-2-aminodiphenyl ether.

19 4"tert.amyl-3-aminodo Do.

diphenyl ether.

T able-Continued No. Diazo component Azo component Shade of wool dyeing20 4-tert.amy1-4-ehlorodo Do.

2 aminodiphenyl ether.

2L 2-rnethyl-4"tert.amyl do Do.

2-aminodiphenyl ether.

22 4'-tert.amyl-4-an1ino( l[(4-ch1oroacetylamino)- Blueish diphenylether. phenoxyacetylamino1-8- red.

hydroxynaphthalene3, fi-disulphonie acid.

23--.. d0 1-[(3-methyl-4-chloroacetyl- Do.

amino)-phenoxyaeetylamino1-8-hydroxynaphthalene-4,6-disnlphonic aci 24--do 1-[(2-methyl-4-chloroacetyl- D0.

amino)- phenoxyacetylamino1-8-hydroxynaphthalene-4,6-disulphonic acid.

25- 4-tert.amyl-2-amino- .d0 Red.

diphenyl ether.

26L ,d0 1-[(3-methyl-4-chloroacetyl- Do.

amino)-phenoxyacetylamino] 8-hydrozwnaphtha1ene-4,6-disu1phonic acid.

27 --do 1-[(3-bromoacetylarnino-4- Do.

methyD-phenoxyacetylamino]-8-hydroxynapthalene-4,6-disulphonic acid.

EXAMPLE 12 parts of previously well wetted wool are entered at 50 into adyebath containing 2 parts of the dyestutf obtained according to Example2 and 6 parts of 30% acetic acid in 3000 parts of water. The bath isbrought to the boil within 15 minutes and boiled for 45 minutes. Theliquor is fully exhausted and a very pure red wool dyeing is obtainedwhich is distinguished by good fastness to light and excellent Wetfastness properties.

What we claim is:

1. The monazo dyestufr" having the general formula R represents a memberselected from the group consisting of alkyl having 4 to 8 carbon atoms,phenyl, benzyl and cyclohexyl,

R represents a member selected from the group consisting of hydrogen andmethyl,

R represents a member selected from the group consisting of hydrogen andmethyl,

X represents a member selected from the group consisting of chlorine andmethyl,

n represents an integer from 0 to 2 inclusive, and

Z represents a member selected from the group consisting ofchloroacetylamino and bromoacetylamino groups.

2. The monoazo dyestuif having the general formula NH-C O-CHz-Cl 3. Themonoazo dyestufi having the formula 5. The monoazo dyestuif having theformula (I) HOaS- I SOSH SOaH 2 I HaCLCCHa HaC--CHs GHQ-OH: (IJHTOHa 4.The monoazo dyestuff having the formula SOaH References Cited in thefile of this patent UNITED STATES PATENTS 2,785,158 Enders et a1 Mar.12, 1957 2,975,167 Schwander et al Mar. 14, 1961 OTHER REFERENCESWegmarm: J. Textil-Praxis, Octpber 1958, pages 1056- 1061.

l NH-C O-CHz-Cl

1. THE MONAZO DYESTUFF HAVING THE GENERAL FORMULA